CN114100623B - Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof - Google Patents
Catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation and preparation method and application thereof Download PDFInfo
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- CN114100623B CN114100623B CN202010868123.2A CN202010868123A CN114100623B CN 114100623 B CN114100623 B CN 114100623B CN 202010868123 A CN202010868123 A CN 202010868123A CN 114100623 B CN114100623 B CN 114100623B
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 42
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 229910021389 graphene Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- 239000012018 catalyst precursor Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- 238000005507 spraying Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- -1 phosphorus compound Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 239000001488 sodium phosphate Substances 0.000 claims description 11
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 11
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 11
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 11
- 150000003682 vanadium compounds Chemical class 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000609 methyl cellulose Polymers 0.000 claims description 9
- 239000001923 methylcellulose Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 8
- 239000005078 molybdenum compound Substances 0.000 claims description 8
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 150000003388 sodium compounds Chemical class 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 239000006012 monoammonium phosphate Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 3
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 3
- LOUBVQKDBZRZNQ-UHFFFAOYSA-M [O-2].[O-2].[OH-].O.[V+5] Chemical compound [O-2].[O-2].[OH-].O.[V+5] LOUBVQKDBZRZNQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 3
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000859 sublimation Methods 0.000 abstract description 2
- 230000008022 sublimation Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 21
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 18
- 239000002245 particle Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 6
- 235000019838 diammonium phosphate Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000005696 Diammonium phosphate Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8874—Gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
The invention discloses a catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation, and a preparation method and application thereof, wherein the catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is a composite carrier comprising a nano carbon material and silicon carbide, the active component comprises a main catalytic component and a co-catalytic component, preferably the main catalytic component comprises vanadium element, molybdenum element, sodium element, phosphorus element and nickel element, and/or the co-catalytic component comprises M element, wherein the M element is at least one of indium element, antimony element and bismuth element. The invention adopts the nano carbon material/silicon carbide as the carrier, can reduce the hot spot of the reaction, reduce the adverse effect of high temperature on the catalyst, lead the catalyst to react at a lower reaction temperature, reduce the sublimation of molybdenum, and is beneficial to maintaining the stability and the service life of the catalyst.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for preparing maleic anhydride by benzene oxidation, in particular to a catalyst for improving selectivity of preparing maleic anhydride by benzene oxidation, and a preparation method and application thereof.
Background
Maleic anhydride (maleic anhydride) is a very important organic chemical raw material, and is the second largest organic anhydride next to phthalic anhydride. The main application of the catalyst is very wide, and the catalyst can be used for producing 1, 4-butanediol, tetrahydrofuran, gamma-butyrolactone, malic acid, unsaturated polyester resin and the like, and can also be used as raw materials of medicines and pesticides. Unsaturated Polyester Resins (UPR) are the largest consumer products downstream of maleic anhydride, and secondly 1, 4-butanediol, both of which can be consumed in amounts of more than 60% of the total maleic anhydride consumed.
The production process of maleic anhydride can be classified into benzene and n-butane method according to the kinds of raw materials. In recent years, the capacity of the device for oxidizing n-butane in China is continuously enlarged, the development trend is faster, but the process for preparing maleic anhydride by the n-butane is more complex than that by using benzene, and the operation is relatively difficult, so that the process using benzene as a raw material can still account for 50% of the total capacity of maleic anhydride.
In areas where coal resources are relatively rich and petroleum resources are relatively poor, the productivity of coal chemical industry is high, a large amount of coking benzene can be generated, and the process for preparing maleic anhydride by taking the coking benzene as a raw material occupies the mainstream process in the areas because of the advantages of the raw material. At present, when the price difference between the benzene raw material cost and the maleic anhydride product is small, the production of enterprises has great competition, so that the economic benefit of the device is improved, the production cost is reduced as much as possible, the benzene consumption is reduced, the byproducts of benzene are reduced, the selectivity of maleic anhydride is improved, and the economic benefit of the device for preparing maleic anhydride by using benzene can be obviously improved.
The reaction for preparing maleic anhydride by benzene oxidation is a severe exothermic reaction, and the V-Mo catalyst plays a very important role in the process of converting benzene into maleic anhydride, and the main preparation process is that active components containing V, mo and auxiliary agents are sprayed on a catalyst carrier, and the catalyst can be prepared by activation. In the preparation process, the carrier has two main functions, namely, the carrier provides support for active components, and the heat generated by the reaction is removed in time, so that higher hot spots are avoided, and the generation of byproducts is reduced. Therefore, the carrier with excellent performance plays a very important role in improving the performance of the catalyst.
Thus, there is a need for a catalyst that can remove the heat of reaction in a timely manner.
Disclosure of Invention
Benzene oxidation to maleic anhydride is a violent exothermic reaction, and if heat generated in the reaction process cannot be removed in time, local overheating can be caused, benzene and maleic anhydride are violently combusted at high temperature, and a large amount of carbon monoxide and carbon dioxide are generated. The invention aims to solve the heat transfer problem of the catalyst in the prior art, adopts a graphene/silicon carbide composite carrier, and utilizes the good heat conduction property of graphene, the low specific surface area and the high strength of silicon carbide to timely remove the heat in the benzene oxidation reaction, thereby improving the performance of the catalyst and ensuring the stability of the catalyst.
The invention aims to provide a catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation, which comprises a carrier and an active component loaded on the carrier, wherein the carrier is a composite carrier comprising a nano carbon material and silicon carbide.
The silicon carbide adopted by the invention has small specific surface area and is suitable for oxidation reaction.
In a preferred embodiment, the nanocarbon material is selected from at least one of graphene, graphite, carbon nanotubes and nanocarbon spheres, preferably graphene.
In a preferred embodiment, the nanocarbon material is present in an amount of 0.001wt% to 8wt%, preferably 0.05wt% to 1wt%, based on 100wt% of the total content of nanocarbon material and silicon carbide.
In a preferred embodiment, the support is prepared by a calcination process at a temperature of 1600 to 2800 ℃ for a period of 0.2 to 8 hours.
In a further preferred embodiment, the calcination temperature is 1800-2500℃for a period of 0.5-5h.
The nano carbon material (especially graphene) is a material with very good heat conduction performance, the heat conduction coefficient of the graphene can reach more than 500W/mK, and the high heat conduction performance can timely conduct out heat generated in the oxidation reaction process, so that the hot spot temperature of a reaction area is reduced, excessive oxidation of benzene and maleic anhydride is prevented, and the performance of a catalyst for preparing maleic anhydride by benzene oxidation is improved. However, although the nano carbon material has a higher specific surface area, if the nano carbon material is used as a carrier, after the active component is loaded on the graphene carrier, the benzene is deeply oxidized to generate more carbon monoxide and carbon dioxide due to the larger specific surface area, so that the selectivity of maleic anhydride is reduced, in addition, the mechanical strength is poor, the active component is not supported easily, the active component is easy to fall off, and the service life of the catalyst is reduced.
Silicon carbide is an inert carrier, and is used for preparing maleic anhydride catalyst by benzene oxidation because of small specific surface area, good heat conduction performance and high mechanical strength. However, the heat conduction performance of the nano carbon material is inferior to that of the nano carbon material, if the nano carbon material is loaded on the silicon carbide carrier, the heat conduction performance of the nano carbon material can be utilized, and the low surface area and high mechanical strength of the silicon carbide can be better utilized, so that the nano carbon material/silicon carbide composite carrier is adopted in the invention and is applied to the reaction of preparing maleic anhydride by benzene oxidation.
In a preferred embodiment, the active component comprises a main catalytic component and a co-catalytic component.
In a further preferred embodiment, the main catalyst component comprises vanadium, molybdenum, sodium, phosphorus and nickel.
In a still further preferred embodiment, the co-catalytic component is an element M selected from at least one of the elements indium, antimony and bismuth.
In a preferred embodiment, the active component is present in an amount of 10wt% to 30wt%, preferably 10wt% to 20wt%, based on 100wt% of the catalyst.
Wherein, the insufficient loading of active components can affect the activity of the catalyst, the too low benzene conversion rate, the too high loading of active components, the serious deep oxidation of the catalyst, more byproducts and the weight yield reduction of maleic anhydride.
In a preferred embodiment, the vanadium element is derived from at least one of metavanadate, orthovanadate, vanadic anhydride, vanadium trichloride, vanadium dioxide, vanadium tetraoxide, preferably metavanadate.
In a preferred embodiment, the molybdenum element is derived from at least one of ammonium molybdate, molybdenum trioxide, calcium molybdate, preferably ammonium molybdate.
In a preferred embodiment, the sodium element is derived from at least one of sodium dihydrogen phosphate, trisodium phosphate, preferably trisodium phosphate.
In a preferred embodiment, the phosphorus element is derived from at least one of monoammonium phosphate, 85% -115% phosphoric acid, phosphorus pentoxide, preferably monoammonium phosphate.
In a preferred embodiment, the nickel element is derived from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel oxide, preferably nickel nitrate.
In a preferred embodiment, the indium element, antimony element and bismuth element are derived from at least one of soluble salts containing the elements.
In a further preferred embodiment, the M element is derived from at least one of acetate, nitrate, chloride, sulfate, bicarbonate, oxalate containing M element.
In a preferred embodiment, the molar ratio of vanadium element, molybdenum element, sodium element, phosphorus element, nickel element and M element is 1 (0.2-0.90): (0.001-0.2): (0.005-0.25): (0.0001-0.05): (0.0001-0.05), wherein V is respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
In a further preferred embodiment, the molar ratio of vanadium element, molybdenum element, sodium element, phosphorus element, nickel element and M element is 1 (0.3-0.80): (0.01-0.1): (0.01-0.1): (0.005-0.03): (0.005-0.02), wherein V is respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
The second object of the present invention is to provide a method for preparing the catalyst according to one of the objects of the present invention, comprising the steps of:
step 1, adding a compound containing an active component into a reducer solution to obtain an active mother solution;
step 2, preparing the carrier by utilizing silicon carbide and a nano carbon material;
step 3, the active mother liquor is contacted with the carrier, and a catalyst precursor is obtained through drying;
and 4, performing activation treatment on the catalyst precursor to obtain the maleic anhydride catalyst prepared by benzene oxidation.
In a preferred embodiment, the active component-containing compounds include a main catalyst component-containing compound and a co-catalyst component-containing compound.
In a further preferred embodiment, the main catalyst component-containing compound includes a vanadium compound, a molybdenum compound, a sodium compound, a phosphorus compound, and a nickel compound.
In a still further preferred embodiment, the co-catalytic component-containing compound comprises an M-containing compound, M being selected from at least one of indium, antimony and bismuth.
In a preferred embodiment, the vanadium compound is selected from at least one of metavanadate, orthovanadate, vanadic anhydride, vanadium trichloride, vanadium dioxide, vanadium tetraoxide, preferably metavanadate.
In a preferred embodiment, the molybdenum compound is selected from at least one of ammonium molybdate, molybdenum trioxide, calcium molybdate, preferably ammonium molybdate.
In a preferred embodiment, the sodium compound is selected from at least one of sodium dihydrogen phosphate, trisodium phosphate, preferably trisodium phosphate.
In a preferred embodiment, the phosphorus compound is selected from at least one of monoammonium phosphate, 85% -115% phosphoric acid, phosphorus pentoxide, preferably monoammonium phosphate.
In a preferred embodiment, the nickel compound is selected from at least one of nickel nitrate, nickel sulfate, nickel chloride, nickel oxide, preferably nickel nitrate.
In a preferred embodiment, the M-containing compound is selected from at least one of the soluble salts containing an M element.
In a further preferred embodiment, the M element is derived from at least one of acetate, nitrate, chloride, sulfate, bicarbonate, oxalate containing M element.
In a preferred embodiment, the molar ratio of vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound and M-containing compound is 1 (0.2-0.90): (0.001-0.2): (0.005-0.25): (0.0001-0.05): (0.0001-0.05), wherein V is respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
In a further preferred embodiment, the molar ratio of vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound and M-containing compound is 1 (0.3-0.80): 0.01-0.1: (0.005-0.03): 0.005-0.02, wherein V is respectively 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
In a preferred embodiment, in step 1, the reducing agent is selected from oxalic acid.
In a further preferred embodiment, in step 1, the molar ratio of the reducing agent to the vanadium compound is (1 to 3): 1, preferably (1.3 to 2.5): 1.
In a preferred embodiment, step 2 comprises the sub-steps of:
step 2.1, dispersing silicon carbide and a nano carbon material in a solvent I, and sequentially stirring and grinding;
step 2.2, drying and roasting in sequence to obtain a composite material;
and 2.3, mixing the composite material with the adhesive and the solvent II, stirring, kneading and forming, and then drying and roasting to obtain the carrier.
In a preferred embodiment, the nanocarbon material is selected from at least one of graphene, graphite, carbon nanotubes and nanocarbon spheres, preferably graphene.
In a preferred embodiment, the nanocarbon material is used in an amount of 0.001wt% to 8wt%, preferably 0.05wt% to 1wt%, based on 100wt% of the total amount of nanocarbon material and silicon carbide.
In a preferred embodiment, the solvent one is selected from the group consisting of water and/or alcohol solvents and optionally amide-based solvents.
In a further preferred embodiment, the alcoholic solvent is selected from methanol and/or ethanol; and/or the amide solvent is at least one selected from dimethylacetamide, dimethylformamide and N, N-dimethylacrylamide.
In a still further preferred embodiment, the amide-based solvent is present in the solvent one in an amount of 0 to 10wt%, preferably 0 to 6wt%.
In a preferred embodiment, in step 2.2, the drying is carried out at 50 to 150 ℃, preferably at 80 to 120 ℃.
In a preferred embodiment, in step 2.2, the firing temperature is 1600-2800 ℃ for a period of 0.2-8 hours.
In a further preferred embodiment, in step 2.2, the calcination temperature is 1800-2500℃for a period of 0.5-5h.
In a preferred embodiment, in step 2.3, the binder is selected from at least one (or at least two or at least three) of china clay, methylcellulose, polypropylene and silica sol.
In a further preferred embodiment, in step 2.3, the weight ratio of the binder to the composite material is from 0.001:1 to 0.2:1, preferably from 0.01 to 0.06:1.
In a preferred embodiment, in step 2.3, the solvent two is selected from water and/or an alcoholic solvent, preferably water.
In a preferred embodiment, in step 2.3, the drying is carried out at 50 to 150 ℃, preferably at 80 to 120 ℃.
In a preferred embodiment, in step 2.3, the calcination is carried out at 700 to 1800 ℃, preferably 900 to 1500 ℃.
In a preferred embodiment, in step 3, the support is subjected to a heat treatment to 180-350 ℃, preferably to 250-270 ℃, prior to said contacting.
Wherein the solvent, especially water, cannot volatilize without heating and the active ingredient cannot adhere to the carrier.
In a preferred embodiment, in step 3, the active mother liquor is contacted with the support in a spray-on manner.
In a further preferred embodiment, in step 3, the spraying is performed at 150-350 ℃, preferably 200-320 ℃, more preferably 250-300 ℃.
Wherein the active mother liquor is sprayed onto the surface of the carrier.
In a still further preferred embodiment, in step 3, the spraying speed is from 0.05 to 1mL/min gcat, preferably from 0.1 to 0.5mL/min gcat.
In a preferred embodiment, the active ingredient-containing compound is present in an amount of from 10% to 30% by weight, preferably from 10% to 20% by weight, based on 100% by weight of the total active ingredient-containing compound and carrier.
In a preferred embodiment, in step 4, the activation treatment is carried out in a closed environment in an activating atmosphere selected from nitrogen and/or helium.
Wherein the catalyst is activated in a closed vessel. The closed container is a cylindrical or square activation furnace body, the upper part of the furnace body is sealed through a flange, the inner space is isolated from the outside, electric furnace wires are wound around the outer wall of the furnace body, heat preservation cloth or heat preservation tiles are arranged outside the electric furnace wires, and the heating temperature of the furnace body is controlled through an automatic digital temperature control meter; the furnace body is provided with a vent from top to bottom, the lower vent is used as a gas inlet, the upper vent is used as a gas outlet, and the flow rate of gas is controlled by a gas mass flowmeter.
In a further preferred embodiment, in step 4, the activation treatment is performed as follows:
4.1 Raising the temperature from room temperature to 150-200 ℃ at a heating rate of 70-150 ℃/h, and keeping for 5-30 minutes;
4.2 Raising the temperature to 220-250 ℃ at a heating rate of 60-120 ℃/h, and keeping for 5-30 minutes;
4.3 Raising the temperature to 300-350 ℃ at a heating rate of 50-100 ℃/h, and keeping for 10-60 minutes;
4.4 Raising the temperature to 420-480 ℃ at a heating rate of 40-90 ℃/h, and maintaining for 5-10 hours;
4.5 And cooling to room temperature at a heating rate of 40-80 ℃/h.
In a still further preferred embodiment, the rate of temperature increase gradually decreases from step 4.1) to step 4.5).
Wherein, through the mode of gradually reducing the rate of temperature rise, the catalyst can be better protected, the performance of catalyst is improved.
The third object of the invention is to provide the application of the catalyst of one of the objects of the invention or the catalyst obtained by the two preparation methods of the object of the invention in preparing maleic anhydride by benzene oxidation.
In a preferred embodiment, the benzene oxidation to maleic anhydride is a molten salt recycle reaction, the molten salt temperature being 340-360 ℃.
Wherein, a molten salt bath is adopted for heating and removing heat.
Wherein, a fixed bed reactor is used in the reaction of preparing maleic anhydride by benzene oxidation, and a molten salt bath is adopted for heating and removing heat. In the evaluation reaction process, the temperatures of the catalyst beds are inconsistent from top to bottom, wherein the highest value of the temperature area is called the hot spot temperature of the catalyst, and the corresponding bed height is the hot spot position of the catalyst. The benzene concentration refers to the number of grams of benzene contained in a unit volume of air, and the higher the number, the higher the benzene content in the air.
In a preferred embodiment, maleic anhydride is prepared by oxidation of benzene with air in a mixed gas of benzene and air through a fixed bed reactor packed with the catalyst.
In a further advantageIn an alternative embodiment, the benzene concentration is 40-55g/Nm during the oxidation of benzene to maleic anhydride 3 。
In a still further preferred embodiment, the volume space velocity of the mixed gas is 1500 to 3000h -1 Preferably 2000-2500h -1 。
In a preferred embodiment, the reaction pressure is negative, normal and pressurized, preferably normal.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The special preparation process is simple in preparation process, easy in raw material acquisition, low in cost and easy in control of the ratio of the nano carbon material to the silicon carbide;
(2) The nano carbon material/silicon carbide composite material is used as the carrier, so that the heat transfer performance of the carrier can be improved, the reaction heat can be timely transferred out, and the heat generated by benzene oxidation reaction can be reduced;
(3) The nano carbon material/silicon carbide is used as a carrier, so that the hot spot of the reaction can be reduced, the adverse effect of high temperature on the catalyst is reduced, the catalyst is enabled to react at a lower reaction temperature, the sublimation of molybdenum is reduced, and the stability and the service life of the catalyst are maintained;
(4) The carrier prepared by the nano carbon material and the silicon carbide in proportion is combined with the addition of the auxiliary agent in the catalyst and the corresponding activation method, so that the selectivity and the yield of maleic anhydride are further improved.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art. The quantitative tests in the following examples were all set up in triplicate and the results averaged.
[ example 1 ]
90g of oxalic acid is dissolved in 480mL of water at room temperature, 65.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, and a uniform and stable solution is formed; dissolving 27.8g of ammonium molybdate in 40mL of 80 ℃ water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.3g of trisodium phosphate, 1.6g of diammonium phosphate, 1.3g of nickel nitrate and 1.2g of indium acetate are added in sequence under stirring, and the mixture is mixed to prepare a catalyst active mother solution.
Taking 0.25g of graphene powder with the average particle size of 1 micron and 499g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide into the mixture, uniformly mixing the mixture, and stirring the mixture for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 8 hours at 100 ℃, roasting for 2 hours at 1800 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form a ring-shaped carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
320g of the carrier is put into a rotary stainless steel drum which can be rotated and heated, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the drum was adjusted to 20 rpm, when the temperature of the support was heated to 250 ℃, the above catalyst active ingredient mixture in the form of a dark green slurry was sprayed onto the support through a special nozzle at 270 ℃ and the support temperature was maintained at 270 ℃, and after the spraying was completed, the catalyst precursor was dried at 100 ℃ for 2 hours, and 383g of the catalyst precursor was weighed to obtain a catalyst precursor having an active material content of 16.4% based on the total mass of the catalyst.
150g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst A.
Catalyst a was charged to the fixed bed reactor and tested using molten salt at 348 ℃ and the results are shown in table 1.
[ example 2 ]
90g of oxalic acid is dissolved in 480mL of water at room temperature, 65.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, and a uniform and stable solution is formed; dissolving 27.8g of ammonium molybdate in 40mL of 80 ℃ water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.3g of trisodium phosphate, 1.6g of diammonium hydrogen phosphate, 1.3g of nickel nitrate and 0.6g of indium acetate are added in sequence under stirring, and the mixture is mixed to prepare a catalyst active mother solution.
Taking 5g of graphene powder with the average particle size of 1 micron and 495g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide by mass, uniformly mixing, and stirring for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 8 hours at 100 ℃, roasting for 2 hours at 2200 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form a ring-shaped carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
320g of graphene/silicon carbide carrier is placed into a rotatable and heatable stainless steel rotary drum, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the drum is regulated to 20 revolutions per minute, when the temperature of the carrier is heated to 250 ℃, the blackish green slurry active component mixture is sprayed on the carrier through a special nozzle, the spraying temperature is 270 ℃, the carrier temperature is kept at 270 ℃, after the spraying is finished, the catalyst precursor is dried at 100 ℃ for 2 hours, 384g of catalyst precursor is obtained by weighing, and the content of the active substance is 16.7 percent based on the total mass of the catalyst.
150g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst B.
Catalyst B was packed in the fixed bed reactor and tested using molten salt at 348 c and the results are shown in table 1.
[ example 3 ]
90g of oxalic acid is dissolved in 480mL of water at room temperature, 65.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, and a uniform and stable solution is formed; dissolving 27.8g of ammonium molybdate in 40mL of 80 ℃ water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.3g of trisodium phosphate, 1.6g of diammonium hydrogen phosphate, 1.3g of nickel nitrate and 1.0g of antimony trichloride are sequentially added under stirring, and the mixture is mixed to prepare a catalyst active mother liquor.
Taking 0.25g of graphene powder with the average particle size of 1 micron and 499g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide into the mixture, uniformly mixing the mixture, and stirring the mixture for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 8 hours at 100 ℃, roasting for 2 hours at 1800 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form a ring-shaped carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
320g of graphene/silicon carbide carrier is placed into a rotatable and heatable stainless steel rotary drum, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the drum is regulated to 20 revolutions per minute, when the temperature of the carrier is heated to 250 ℃, the blackish green slurry active component mixture is sprayed on the carrier through a special nozzle, the spraying temperature is 270 ℃, the carrier temperature is kept at 270 ℃, after the spraying is finished, the catalyst precursor is dried at 100 ℃ for 2 hours, 384g of catalyst precursor is obtained by weighing, and the content of the active substance is 16.7 percent based on the total mass of the catalyst.
150g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst C.
Catalyst C was packed in the fixed bed reactor and tested using molten salt at 348℃ and the results are shown in table 1.
[ example 4 ]
90g of oxalic acid is dissolved in 480mL of water at room temperature, 65.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, and a uniform and stable solution is formed; dissolving 27.8g of ammonium molybdate in 40mL of 80 ℃ water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.3g of trisodium phosphate, 1.6g of diammonium hydrogen phosphate, 1.3g of nickel nitrate and 0.5g of antimony trichloride are added in sequence under stirring, and the mixture is mixed to prepare a catalyst active mother liquor.
Taking 5g of graphene powder with the average particle size of 1 micron and 495g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide by mass, uniformly mixing, and stirring for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 8 hours at 100 ℃, roasting for 2 hours at 2300 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form a ring-shaped carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
320g of graphene/silicon carbide carrier is placed into a rotatable and heatable stainless steel rotary drum, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the drum is regulated to 20 revolutions per minute, when the temperature of the carrier is heated to 250 ℃, the blackish green slurry-like active component mixture of the catalyst is sprayed on the carrier through a special nozzle, the spraying temperature is 270 ℃, the carrier temperature is kept at 270 ℃, after the spraying is finished, the catalyst precursor is dried at 100 ℃ for 2 hours, 386g of the catalyst precursor is weighed, and the content of the active substance is 17.1 percent based on the total mass of the catalyst.
150g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst D.
Catalyst D was packed in the fixed bed reactor and tested using molten salt at 348 ℃ and the results are shown in table 1.
[ example 5 ]
90g of oxalic acid is dissolved in 480mL of water at room temperature, 65.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, and a uniform and stable solution is formed; dissolving 27.8g of ammonium molybdate in 40mL of 80 ℃ water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.3g of trisodium phosphate, 1.6g of diammonium phosphate, 1.3g of nickel nitrate and 1.0g of bismuth nitrate are added in sequence under stirring, and the mixture is mixed to prepare a catalyst active mother liquor.
Taking 5g of graphene powder with the average particle size of 1 micron and 495g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide by mass, uniformly mixing, and stirring for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 8 hours at 100 ℃, roasting for 2 hours at 1800 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form a ring-shaped carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
320g of graphene/silicon carbide carrier is placed into a rotatable and heatable stainless steel rotary drum, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the drum was adjusted to 20 rpm, when the temperature of the support was heated to 250 ℃, the above catalyst active ingredient mixture in the form of a dark green slurry was sprayed onto the support through a special nozzle at 270 ℃ and the support temperature was maintained at 270 ℃, and after the spraying was completed, the catalyst precursor was dried at 100 ℃ for 2 hours, and 383g of the catalyst precursor was weighed to obtain a catalyst precursor having an active material content of 16.4% based on the total mass of the catalyst.
150g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst E.
Catalyst E was packed in the fixed bed reactor and tested using molten salt at 348℃and the results are shown in Table 1.
[ example 6 ]
90g of oxalic acid is dissolved in 480mL of water at room temperature, 65.6g of ammonium metavanadate is added while stirring until the ammonium metavanadate is dissolved, and a uniform and stable solution is formed; dissolving 27.8g of ammonium molybdate in 40mL of 80 ℃ water to be uniformly dissolved, and adding the solution into the ammonium metavanadate solution; 4.3g of trisodium phosphate, 1.6g of diammonium phosphate, 1.3g of nickel nitrate and 1.0g of bismuth nitrate are added in sequence under stirring, and the mixture is mixed to prepare a catalyst active mother liquor.
Taking 5g of graphene powder with the average particle size of 1 micron and 495g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide by mass, uniformly mixing, and stirring for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 8 hours at 100 ℃, roasting for 2 hours at 2400 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form a ring-shaped carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
320g of graphene/silicon carbide carrier is placed into a rotatable and heatable stainless steel rotary drum, a thermowell is arranged at the bottom of the carrier, and an internal thermocouple is connected with a temperature display instrument to display the temperature change in the spraying process in real time. The rotation speed of the drum was adjusted to 20 rpm, and when the temperature of the support was heated to 250 ℃, the above catalyst active ingredient mixture in the form of a dark green slurry was sprayed onto the support through a special nozzle at 270 ℃ and maintained at a temperature of 270 ℃, and after the spraying was completed, the catalyst precursor was dried at 100 ℃ for 2 hours, and 385g of the catalyst precursor was weighed to obtain a catalyst precursor having an active material content of 16.9% based on the total mass of the catalyst.
150g of the above catalyst precursor was placed in an activation furnace, sealed, and then heated from room temperature to 150℃at a heating rate of 150℃per hour for 5 minutes, then heated to 250℃at a heating rate of 120℃per hour for 10 minutes, then heated to 350℃at a heating rate of 100℃per hour for 20 minutes, then heated to 450℃at a heating rate of 90℃per hour for 5 hours, and then gradually cooled to room temperature, to obtain catalyst F.
Catalyst F was packed in the fixed bed reactor and tested using molten salt at 348℃and the results are shown in Table 1.
Comparative example 1
Catalyst G was prepared in the same manner as in example 1, except that the graphene material was not added, and then the carrier was prepared, and then spray coating and drying were performed, to obtain 384G of a catalyst precursor, the content of the active material being 16.7% based on the total mass of the catalyst.
Catalyst G was packed in the fixed bed reactor and tested using molten salt at 348 ℃ and the results are shown in table 1.
Comparative example 2
Catalyst H was prepared in the same manner as in example 1 except that no calcination treatment was used in the preparation of the support, and no composite material was obtained, except that mechanical mixing was performed:
taking 0.25g of graphene powder with the average particle size of 1 micron and 499g of silicon carbide powder with the average particle size of 1 micron, adding an ethanol solution of 2% of dimethylacetamide into the mixture, uniformly mixing the mixture, and stirring the mixture for 1h, wherein the corresponding rotating speed is 500r/min; grinding for 12 hours on a ball mill, drying for 10 hours at 100 ℃ to obtain a graphene/silicon carbide composite carrier, adding 400g of the composite carrier, 100g of porcelain clay, 33g of methylcellulose and 64g of polypropylene into 100mL of water, mixing, stirring and kneading to form an annular carrier, drying for 8 hours at 100 ℃, and roasting for 5 hours at 1200 ℃.
[ comparative example 3 ]
Catalyst I was prepared in the same manner as in example 1 except that no silicon carbide material was added, and it was found that the carrier was not easily molded during processing when only graphene was used, the processability was poor, and the spraying effect was very poor when the active component was sprayed. In addition, because of the large specific surface area of the graphene, benzene can be deeply oxidized to generate more carbon monoxide and carbon dioxide, the selectivity of maleic anhydride is reduced, in addition, the mechanical strength is also poor, the active components are not easy to load, the active components are easy to fall off, and the service life of the catalyst is reduced.
[ catalyst evaluation ]
And (3) filling the catalyst activated by the activation furnace into a 120mL bubbling molten salt circulating reactor, wherein the bottom of the reactor is supported by an inert carrier, the middle of the reactor is filled with 120mL of catalyst, and the upper part of the reactor is provided with the inert carrier with a certain height. When the molten salt is heated to the temperature required by the reaction, air is fed, benzene is simultaneously fed, and after the benzene concentration reaches the concentration of the required working condition, sampling analysis is started after the benzene concentration is stabilized for 1 hour, and the sampling evaluation results of each catalyst are shown in table 1.
The calculation method of each index is as follows:
benzene conversion (%) = (amount of benzene at reactor inlet per unit time-amount of benzene at reactor outlet per unit time)/amount of benzene at reactor inlet per unit time x 100%
Maleic anhydride weight yield (%) =benzene conversion x maleic anhydride selectivity x 98/78 x 100%
TABLE 1 results of 120mL single tube Activity evaluation
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (29)
1. A catalyst for improving selectivity of maleic anhydride prepared by benzene oxidation comprises a carrier and an active component loaded on the carrier, wherein the carrier is a composite carrier comprising a nano carbon material and silicon carbide; the nano carbon material is at least one of graphene, graphite, carbon nano tube and nano carbon sphere, and the content of the nano carbon material is 0.001-8wt% based on 100wt% of the total content of the nano carbon material and silicon carbide; the carrier is prepared as follows: dispersing silicon carbide and a nano carbon material in a solvent I, and sequentially stirring and grinding; then drying and roasting are sequentially carried out to obtain a composite material; roasting at 1600-2800 ℃ for 0.2-8 hours; mixing the composite material with a binder and a solvent II, stirring, kneading and forming, and then drying and roasting to obtain the carrier.
2. The catalyst of claim 1, wherein the catalyst is,
the nanocarbon material is selected from graphene.
3. The catalyst of claim 1, wherein the catalyst is,
the content of the nano carbon material is 0.05wt% to 1wt% based on 100wt% of the total content of the nano carbon material and the silicon carbide.
4. The catalyst of claim 1, wherein the calcination temperature is 1800-2500 ℃ for a period of 0.5-5 hours.
5. The catalyst according to any one of claims 1 to 4, wherein the active component comprises a main catalytic component and a co-catalytic component, the main catalytic component comprises vanadium element, molybdenum element, sodium element, phosphorus element and nickel element, and/or the co-catalytic component comprises M element, the M element being at least one selected from indium element, antimony element and bismuth element.
6. The catalyst of claim 5, wherein the active component is present in an amount of 10wt% to 30wt%, based on 100wt% of the catalyst.
7. The catalyst according to claim 6, wherein the content of the active component is 10wt% to 20wt%, based on 100wt% of the catalyst.
8. The catalyst according to claim 5, wherein the molar ratio of vanadium element, molybdenum element, sodium element, phosphorus element, nickel element and M element is 1 (0.2-0.90): (0.001-0.2): (0.005-0.25): (0.0001-0.05): (0.0001-0.05); wherein, respectively by V 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
9. The catalyst according to claim 8, wherein the molar ratio of vanadium element, molybdenum element, sodium element, phosphorus element, nickel element and M element is 1 (0.3-0.80): (0.01-0.1): (0.01-0.1): (0.005-0.03): (0.005-0.02); wherein, respectively by V 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
10. A method for preparing the catalyst according to any one of claims 1 to 9, comprising the steps of:
step 1, adding a compound containing an active component into a reducer solution to obtain an active mother solution;
step 2, preparing the carrier by utilizing silicon carbide and a nano carbon material; the nano carbon material is at least one selected from graphene, graphite, carbon nano tubes and nano carbon spheres;
step 3, the active mother liquor is contacted with the carrier, and a catalyst precursor is obtained through drying;
step 4, activating the catalyst precursor to obtain the maleic anhydride catalyst prepared by benzene oxidation;
step 2 comprises the following sub-steps:
Step 2.1, dispersing silicon carbide and a nano carbon material in a solvent I, and sequentially stirring and grinding;
step 2.2, drying and roasting in sequence to obtain a composite material; in the step 2.2, the roasting temperature is 1600-2800 ℃ and the time is 0.2-8h;
and 2.3, mixing the composite material with the adhesive and the solvent II, stirring, kneading and forming, and then drying and roasting to obtain the carrier.
11. The method according to claim 10, wherein,
the active component-containing compounds include a main catalyst component-containing compound and a co-catalyst component-containing compound; the compound containing the main catalyst component comprises a vanadium compound, a molybdenum compound, a sodium compound, a phosphorus compound and a nickel compound; and/or the compound containing the promoting component comprises an M-containing compound, M being at least one selected from indium, antimony and bismuth; and/or
The content of the active ingredient-containing compound is 10wt% to 30wt% based on 100wt% of the total amount of the active ingredient-containing compound and the carrier.
12. The method according to claim 11, wherein,
the content of the compound containing the active component is 10-20 wt% based on 100wt% of the total amount of the compound containing the active component and the carrier.
13. The method according to claim 11, wherein,
the vanadium compound is at least one selected from metavanadate, orthovanadate, vanadium pentoxide, vanadium trichloride, vanadium dioxide and vanadium tetraoxide; and/or
The molybdenum compound is at least one selected from ammonium molybdate, molybdenum trioxide and calcium molybdate; and/or
The sodium compound is at least one selected from sodium dihydrogen phosphate and trisodium phosphate; and/or
The phosphorus compound is at least one selected from monoammonium phosphate, 85% -115% phosphoric acid and phosphorus pentoxide; and/or
The nickel compound is at least one selected from nickel nitrate, nickel sulfate, nickel chloride and nickel oxide; and/or
The M-containing compound is at least one selected from soluble salts containing M elements.
14. The method according to claim 11, wherein the molar ratio of the vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound and M-containing compound is preferably 1 (0.2-0.90): (0.001-0.2): (0.005-0.25): (0.0001-0.05): (0.0001-0.05); wherein, respectively by V 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
15. The method according to claim 14, wherein the molar ratio of the vanadium compound, molybdenum compound, sodium compound, phosphorus compound, nickel compound and M-containing compound is preferably 1 (0.3-0.80): (0.01-0.1): (0.01-0.1): (0.005-0.03): (0.005-0.02); wherein, respectively by V 2 O 5 Molar amount, in MoO 3 Molar amount of Na 2 O molar amount, in terms of P 2 O 5 Molar amount, in terms of NiO molar amount, in terms of M element molar amount.
16. The method of claim 11, wherein in step 1, the reducing agent is selected from oxalic acid.
17. The method according to claim 16, wherein the molar ratio of the reducing agent to the vanadium compound is (1-3): 1.
18. The method according to claim 16, wherein the molar ratio of the reducing agent to the vanadium compound is 1.3 to 2.5:1.
19. The method of claim 10, wherein, in step 2.1,
the amount of the nano carbon material is 0.001-8wt% based on 100wt% of the total amount of the nano carbon material and the silicon carbide; and/or
The solvent one is selected from water and/or alcohol solvents and optional amide solvents.
20. The method of claim 19, wherein, in step 2.1,
the dosage of the nano carbon material is 0.05wt percent to 1wt percent based on 100wt percent of the total dosage of the nano carbon material and the silicon carbide; and/or
The alcohol solvent is selected from methanol and/or ethanol, and/or the amide solvent is selected from at least one of dimethylacetamide, dimethylformamide and N, N-dimethylacrylamide.
21. The method according to claim 19, wherein the amide solvent is more preferably present in the first solvent in an amount of 0 to 10wt%.
22. The method according to claim 10, wherein,
in the step 2.2, the drying is carried out at 50-150 ℃; and/or
In the step 2.2, the roasting temperature is 1800-2500 ℃ and the time is 0.5-5h; and/or
In step 2.3, the binder is selected from at least one of china clay, methylcellulose, polypropylene and silica sol; and/or
In step 2.3, the solvent two is selected from water and/or alcohol solvents; and/or
In the step 2.3, the drying is carried out at 50-150 ℃; and/or
In the step 2.3, the roasting is performed at 700-1800 ℃.
23. The method of claim 22, wherein the process comprises,
In the step 2.2, the drying is carried out at 80-120 ℃; and/or
In the step 2.3, the weight-to-weight ratio of the adhesive to the composite material is 0.001:1-0.2:1; and/or
In step 2.3, the second solvent is selected from water; and/or
In the step 2.3, the drying is carried out at 80-120 ℃; and/or
In the step 2.3, the roasting is performed at 900-1500 ℃.
24. The method according to claim 10, wherein,
in the step 3, before the contact, heating the carrier to 180-350 ℃; and/or
In step 3, the active mother liquor is contacted with the carrier in a spray coating manner; and/or
In the step 3, the dosage ratio of the active mother liquor to the carrier is 1.0:1-3.5:1.
25. The method of claim 24, wherein the process comprises,
in step 3, the carrier is heated to 250-270 ℃ before said contacting; and/or
In step 3, the spraying is performed at 150-350 ℃; and/or
In the step 3, the dosage ratio of the active mother liquor to the carrier is 1.5-2.5:1.
26. The method of claim 25, wherein the process comprises,
in the step 3, the spraying speed is 0.05-1mL/min gcat.
27. The method according to claim 26, wherein in the step 3, the spraying speed is 0.1 to 0.5ml/min gcat.
28. The method according to any one of claim 10 to 27, wherein,
in the step 4, the activation treatment is carried out in a closed environment and an activation atmosphere, wherein the activation atmosphere is selected from nitrogen and/or helium; and/or
In step 4, the activation treatment is performed as follows:
4.1 Raising the temperature from room temperature to 150-200 ℃ at a heating rate of 70-150 ℃/h, and keeping for 5-30 minutes;
4.2 Raising the temperature to 220-250 ℃ at a heating rate of 60-120 ℃/h, and keeping for 5-30 minutes;
4.3 Raising the temperature to 300-350 ℃ at a heating rate of 50-100 ℃/h, and keeping for 10-60 minutes;
4.4 Raising the temperature to 420-480 ℃ at a heating rate of 40-90 ℃/h, and maintaining for 5-10 hours;
4.5 And cooling to room temperature at a rate of 40-80 ℃/h.
29. Use of the catalyst according to any one of claims 1 to 9 or the catalyst obtained by the preparation method according to any one of claims 10 to 28 for preparing maleic anhydride by benzene oxidation.
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| CN107774287A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of loaded catalyst and its preparation for benzene oxidatoin cis-butenedioic anhydride |
| CN109201095A (en) * | 2017-07-04 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of benzene oxidatoin catalyst for preparing cis-anhydride and the preparation method and application thereof |
| CN108607587A (en) * | 2018-03-22 | 2018-10-02 | 江苏金聚合金材料有限公司 | A kind of preparation of big hole silicon carbide/graphene mixed carrier loaded palladium catalyst |
| CN109395755A (en) * | 2018-10-24 | 2019-03-01 | 中南大学 | A kind of Heat Conduction Material doping vanadium-phosphor oxide catalyst and preparation and the application in normal butane selective catalytic oxidation synthesis cis-butenedioic anhydride |
| CN109731594A (en) * | 2019-02-28 | 2019-05-10 | 中国科学院过程工程研究所 | A kind of preparation and application of vanadyl phosphate catalyst |
| JP6706404B1 (en) * | 2019-08-21 | 2020-06-10 | 南京大学 | Carbon nanotube ozone catalyst suitable for high pH and its use |
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